DE2524578B2 - 5-HYDROXYLAMINOMETHYLENE BARBITURIC ACID DERIVATIVES, PROCESS FOR THEIR PRODUCTION AND USE AS HERBICIDE - Google Patents

Description

OH

R ₁ CR ₁

O ()

R-

wherein R ₁ , R ₂ and R _{3 have} the above meaning with a compound of the formula

R ₄ -O-NH ₂

wherein R _{4 has} the above meaning, is reacted in a manner known per se.

3. Use of the compounds of claim 1 as active ingredients in herbicides or Vermin · ¹ ling control agents conventional composition.

The invention relates to 5-hydroxylamino- ethylenbarbituric acid derivatives. to a process for their production and their use in species cultivation and agriculture, in particular s selective herbicides.

In DT-OS 21 33 049 are barbituric acid derivatives l given. as pesticides as well as Suitable for combating plant diseases. It is also stated that these compounds : Soiien have rbicidal efficacy. However, this effect does not affect the treatment of broad-leaved dishonesties limited after emergence.

Hs is the object of the present invention, new crbicide means to develop which is also a good one have kiixitäl before emergence.

The invention relates to 5-Hydroxylaminomelhylenbarbiiursäurederivaie of the general formula I.

NHC) R,

R ₁ C

R ₁ 111

ο ο

R,

worm R ₁ and R, each a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. R, is an alkyl group with 1 to 3 carbon atoms and R _{4 is} an ether group, as well as the metal salts of the above compounds in which at least one of the radicals R ₁ and R is a hydrogen atom.

Those compounds in which R ₁ and R _{1 are} hydrogen atoms and R 1 represents an alkali group having 2 or 3 carbon atoms are preferred.

The compounds according to the invention have a good, in some cases even high-grade herbicidal action on what is especially true for 5- (l-AUyloxyaminopropylidenebarbituric acid and the 5- (l-ethoxyaminopropylidene) barbi: ursic acid applies. Besides this effect as selective herbicides, the compounds also have acaricidal and insecticidal effects. so that she is a can find extensive use in horticulture and agriculture.

The compounds according to the invention are prepared according to the following equation:

HO

C R.

R ₄ O NlL

(111)

NH OR ₄

N ■■■
OO

R.

ill

wherein R ₁ to R _{4 have} the above meaning.

The reaction is best carried out in an inert solvent at a temperature between room temperature and the boiling point of the solvent in question, preferably between 30 and 60.degree DieRe;: ktioüsdai! Er is IS minutes to 3 hours. After the reaction, the solvent becomes optional replaced by another, whereupon the reaction gcmisch Washed with dilute alkali and water and dried: after distilling off of the solvent obtained under reduced pressure

the raw product as crystals or in liquid p) m It can be recrystallized or on be purified by the minimal and spiritual way.

Pie of the invention also included sodium

d Potassium salts are produced by i

^Ü L · Compound · according to formula 1 in aqueous solution .mg

an organic solvent with natural

Treated 1 r potassium hydroxide and isolate the salts by filtering off or concentrating the solution. the r-ilcium- barium, manganese. Copper-. Zinc-. Nickel-. W ib ill- iron and silver salts can be obtained from the Nhirium salt by treating with a salt of h corresponding metal, e.g. B. with calcium or barnim chloride. Copper sulfate, zinc or nickel chloride or Kobalt Nitrai. obtain.

The calcium salt can also be used directly lid by making the connection after Formula 1 treated with calcium hydroxide.

The compounds according to formula 1 can m tautonrren Forms "exist. For their notation /.B. The following possibilities exist:

NU O- R ₄

C)

C)

R-

111

NC) R _:

R,

C) H

N
R,

N \
N \?
R,

IVi

N - ■ C) R ₄

(V)

The invention is explained in more detail with the aid of the examples.

Example 1 5- (l-Allyloxvaminopropylidene) -barbiUn acid

1 S H 5-I'ropionylbarbituric acid

Dissolved dimethylformamide and heated to 40 C, whereupon 1.5 g of allvloxvamin were added and the resulting solution was stirred at 40 ° C. for 3 hours Then it became about 10 ml of dimethylformamide distilled off and replaced by 50 ml Albuno], whereupon crystals separate out, the aniline ici i and off Ethanol were recrystallized. There were 2.1 g of the above compound in the form of white crystal columns obtain. Mp. 172 to 173 C (decomposition!; Howling: 72%.

Example 2

5- (l-ethoxyaminoethylidene) -1,3-dimethylbarbituric acid

1.5 g of 5-acetyl-1,3-dimethylbarbituric acid were dissolved in 50 ml of ethanol and 5 ml of ethowamine were added to the solution. After stirring for 2 hours at 40 ° C., the solution was left to stand for a few cells at room temperature. White plates separated out. which were filtered off and recrystallized from ethanol. 1.4 g of the above compound were obtained; M.p. 143 145 ^C C; Yield: 58%. "

Example 3

5- (1-Allyloxyaminopropylidene I-1,3-dimethylbarbituric acid

2.1 g 1,3-dimethyl-5-propionyl barbi! U! Säjre »orden Dissolved in 30 ml of ethanol and added 1 μ of allyloxyamine to the solution. After stirring for 2 hours The ethanol was distilled off at room temperature. white crystals separated out and were recrystallized from methanol. 2.3 g were obtained the obisen connection as white crisp pillars. M.p. 56-58 C; Yield: 86%.

Example 4

5- (1-Allyloxyaminobutylidene) -1.3-dimethylbarbituric acid

2.3 g of 5-butyryl-1,3-dimethylbarbituric acid were dissolved in 30 ml of ethanol and the solution was dissolved at 30 ° C. with 1 g of allvloxvamin / ugesei / l. After stirring for 2 seconds, the ethanol was distilled off. where you see white crystals deposit. 2.6 g of the above compound were obtained, which, after crystallization from methanol, was present in the form of crystal needles. Fp. 5 ^l ) '■> ** C': Howling: 93 "...

Aul.ier -Jen compounds mentioned in Examples i to 4 those listed in Table I were prepared and examined.

Table I.

Vlm am-
1 5- (I-Allvlo \ vaminopro-
p \ liden l-barbiiursäiire l'llVMk.ll
K t M1 ^ Ί, H11 l'I 1 I- C lHIII'J
\ l 5-11 -Athowaminoäthv-
lidenl-barbituric acid 2IUi C I. 5-11-Atho \\ aminoäth \ -
lidenl-1.3-dimeth \ l- M.p. 172
I dec. I. 145 C barbiluric acid M.p. 204
(Dec. I. 5- (1 -Athowaniinopro-
p \ liden i-barbaric acid M.p. 143
I dec. ι ISd ( 5-1 l-. ^: \ tho \ _vamino-2-me-
thv lprop \ liden i-1.3-di-
meihv ibricuric acid n: c 4th 5-t I -Athowaniinopro-
p> liden I- 1.3-dimeih \ l- M.p. 1S4
(Zers ι "S ( harbituric acid Fp. I'M
(Dec. Ι (> 5-1! - All> lo \\ aminopri> -
pv liden ι-1.3-dimeth \ T Ip Th
ι decomp. ι 5 N ( barbicuric acid Tp. 5 (»

5- <1-AlIv low aminobulv-

liden) -1.3-dimethvl-

harbituric acid

1 -ι -Bu ". \ L-3-mciliyl-

5- (l-aiho \ vaminopro-

p \ lidenlbarbituric acid

5-1I-Älho \ vaminopro-

pylidenH-meihvl-

barbituric acid c

5-1! -Alhlowaminobuly-

lidcnl barbaric acid

5- (1-Alho \ vaminobutv-

lidcnlbiirbituric acidc

5- (1-Allvloxvaminobuiv-

lidcnl-l-melhvl-

harhiluric acid

5-11-ally loxyaminopro-

pvlidcn) -l-meth \ l-

barbiluric acid

Sodium sal / of

5-1 I-allyloxyamino

propvlidenl-

barbiluric acid c

Calcium sal / \ on

5-1 l-AlKlowamino-

propvlidenl-

barbituric acid c

Copper salt of

5-1I-allyloxvamino-

propvlidcn) -

barbilursäuie

Potassium sal / of

5- (l-.Ml * lowamino-

hiilν liclcn) hai bitnrsiuirc

Nalrinmsal / from

5- (I-Älhoxvamino-

butylidene barboric acid

Calcium salt of

5- <Allvlo \ vamino-

butvlidcnlbarbilursäuie

Copper salt of

5-11-Alls lowamino-

butylidenelbarbituric acid

l'lnsik.l

M.p. 54 W) C

; i 1.5232

I-'p. 129 131 C

! • p. 1S4 185 C

I-'p. 19S IW C

I Zcrs.)

M.p. 133 134 C

I-'p. 130 131 C

M.p. 27 *) C.

M.p. 270 C.

Ip. 27 (1c

I-'p. 2 (i3 264 C (Zcrs.)

Ip. ti, loaded. 250 (Ί / .ers.)

F'p. 270 C

Fp. U) S IW C I / .eis. I.

As already noted, the inventive r, Compounds have a particularly high herbicidal effect. Their use as active ingredients is described below described in more detail in I 'nkraulbekiinipfungsmilleln.

Particularly effective are the compounds / in control of grassy ^I: nkräuiern: Examples are: wi annual bluegrass (Poa aniiua I). Water lynx swan / lAlopecurus aequalis Sobol). great linucikraul (Digitaria adscendcns Henr.). green fox-M.-h \\ an / iSciiiria \ iridis !. W'ildhafor!. · \\ en ;! l'aiua I ι etc .; on the other hand they attack Hreilblalipllan / s. like t "i Ad / ukibeans ll'haseolus angulans W. 1 ^:. Wight) and soybeans i (il \ cine ma \ Merrill ι as well as / uckcrrüben (Beta vulgaris L.). which are otherwise very sensitive

are hardly on. In this respect, they are tolerable Compounds selective herbicides.

If the compounds according to the invention are used for leaf treatment. so grab yourself in one Amount in which they are in (icmiisepflan / ungen I liihncilnrse Unsolder completely, double-leaf groove / plan / s. how Radish (Raphanus sativus L.). Soybean. Garden pea (Pisum sativum L.). Spinach (Spinacia oleracea L.). Sugar beet and carrots (Daueus carola Li at all not on: the same applies to treatment \ ni emergence, even if the active ingredients are used in a menu in which they germinate /.B. completely prevent urol.lem cinquefoil

The l'hvioio \ i / itäi of the compounds opposite Paperboard plans are therefore extremely small: with regard to animal application / speed. of the application and the concentration to be applied is free. Since the funds are already in lower Concentration is effective, too, is not poisoning of the soil or the plant and just as little danger to warm-blooded animals or fish.

The compounds according to the invention can be used directly in the ground before the emergence of the animal hall, or you can put them after the AuIIaUIeH apply to the plants themselves. in the In the icier case, they are mixed intimately with the FuIc. with a ratio of 50 to 1000 g of active ingredient each IO Ar. preferably IOP up to 400 g per 10. \ r and in particular 200 g per 10 ares is appropriate.

The Iikiatilbekämpfungsmiltel. making the connections Adhere to as an active ingredient, can be used in liquid or solid state. /. B. as wettable släubmillel. emulsifiable concentration or in the form of fine powder or (iranulaien. water-soluble powders or aerosols. As solid carriers to serve /. B. Bentonite. Diaiome earth. Apatite, dips. Talk. Pv rophvllil. Vermiculite. Clay and others. Light mineral oils are used as liquid Iranians. Frdöl. Solventnaphlha. Benzene. Xylene. C'vclohexane. Cvchhexanone. Diinetliv! Formamid. Alcohol. Acetone. Water etc. If necessary, use it for homogenization and stabilizing a surfactant to it. The connections according to the invention can also be mixed with other chemicals used in agriculture or plant breeding used and compatible with them. Examples of such additives are plant nutrients. Fertilizer. Insecticide c. Acaricide. Fungicide. Nemalocide and other herbicides.

As known herbicides, those with the erliiulungsgemeinschaft Active ingredients can be mixed, urea derivatives are recommended, z. B. 3- (3.4-dichlorophenv 11-1-methoxv -1 -methylurea or N-13.4-dich lorphcnvUN '. N-dimethyl urea, or triazine derivatives. w ic 2-chloro-4-ethylamino-6-isopropyl laminos-triazine or 2-chloro-4,6-bis- (ethylamino) -s-inazine and amide derivatives. such as N-1-naphthylphthalamino acid.

The concentration in which the compounds according to the invention are present as active ingredients in the herbides depends on various factors. 60 Crew.- ⁰ O. in emulsifiable concentrates from 5 to> 30. preferably from 20 to 60 wt .-%, and in dusts in a concentration of 0.5 to 30. Preferably, from 1 to 10 Gevv .-% . to be available.

Wettable powder or emulsifiable concentrate »

λ ground with water to a certain concentration .thinned, and the remedy thus prepared becomes liquid Suspension or emulsion in the soil or applied to uiic plants. Dusts become unsuitable for waste on the ground or on the leaves

With the help of the experiments described below ν- in de the effectiveness of the agents according to the invention tried.

Attempt 1
Treatment of the soil before emergence

! • about 60 grains of chicken millet were in a pot with a surface of 60 cm was placed and lightly covered with earth. After moistening the

Earth with water was sprayed with 10 ml of an aqueous emulsion obtained by Dilute the emulsifiable concentrate in question with water to a specific concentration. The pots were kept moist in the greenhouse and 3 weeks after spraying it was determined to what extent the plants were damaged. The grading was carried out according to the following scheme:

0 = no effect.

1 = parts of the plant slightly damaged.

2 = Plant slightly damaged overall.

3 = medium severely damaged plant.

4 = plant badly damaged.

5 = plant completely killed or no germination.

The results are shown in Table 11.

Tabel

Application amount in g 10 ar 1000 120

30th

1?

bind N'r.

4th 5

3 0 0 3 0 0 0

Comparison compounds

STILL ₁ -CH =

* l

OH

O'%

CH,

O
HI ¹ COCH ₃

O N H Ό Hf O H Ii COC; ■ '\

-, C ■■■■ COC, H- (
N \

N
0 HO

709Mi

Forlsetzunu

Comparison compounds
O

COCH ₃

H ₁ C Il COCH,

VN-

CH ₁

Untreated

· | Japan. Patent Application No. 46-16916 (published). *) DT-OS 21 33 049.

ίο

Application amount in g / 10Ar 1 (XX) 120 60

30th

15th

Attempt 2
Treatment before emergence

Large cinquefoil seeds were placed in a pot with a HK) cnr surface and sprayed with 5 ml of an aqueous emulsion that

Table 111

obtained svar by diluting an emulsifiable Concentrates with water. After 21 days in the greenhouse, the degree of damage became apparent svie determined above.

The results are shown in Table III.

Test compound # 1

Untreated Verification bond

OH

STILL, —CH = CH,

CH ₁

H ₁ C

Application amount 125 in g / 10 ares 0 0 -> 250 4th 62.5 31.3 0 5 3 3 4th 4th 1 0 S. -) 3 0 4th 3 0 4th 1 0 1 4th

Attempt 3

Treatment after the AuHaIiIeIi I Hhil t treatment η l; ι As above, in pots of KKl cnr surface

Grains of big cinquefoil aiiehrachi. After the plants had risen and formed from 2 to 4 leaves hold "ere .They with an aqueous Fmulsion sprayed, the erhallen ss orden ssary tiurcli dilution / enir.iiion an emulsifiable Kon / mil entraies water to the corresponding Kon. Λ ^'1'

U 12

Spray was used in an amount that determined how far the plants were damaged. 100 1 ie 10 Ar corresponded. The results are shown in Table IV.

became like above

Table IV

Test compound # 1

2 3 4 6 7

Application amount in

g / 10 ares

100 50 25

5 4 4 5 4 5 5

5 2

2 5 2 4 4

4 0 0 4 0 2

Comparison compounds

STILL ₁ -CH = CH ₂ OH /

attempt

leaves of potted beans ^ 10 days after germination freight £ "<- η _; later, not S "unde ⁿ ^ u IJbtn plant have been removed. Then the IM an * en were obtained by diluting an enu.1 born kο ze ηt with water aqueous suspu ^ si ^. the connection to be tested. mJX _m ^ _p contained 0.05%, spray !. 3 Tc ^ na _{and dic}

a - number of live mites on untreated

Plants. h = number of surviving mites on treated egg

Plants.

Efficiency in%: '———- ·

ti = number of eggs laid.

b ' = number of animals that have escaped.

Based on the above counts, the test compounds were graded as follows:

.-true: r .- 'i

Mortality in ° «:

100 mortal wedge b / w \ Virkun;: \ t: niiJ

100 ",,

St) ¹ W ",,

7 ') ",,

1) ιΜΐ <πι: ιμ

13 V

The results are shown in Table V.

Table V

Leased line
No.

Seriousness

in %

Test connection

Mortality impact after after

3 days 11 days

2.4.5.4 -Tetrachloridphcnylsulfon (comparison)

Attempt 5
Effectiveness as an insecticide against flies

In a cage with 20 male and 20 female adult houseflies (Musca domeslica) as feed, a mixture of 49% milk powder, 49% sugar and 1% of the compound to be examined plus water brought in.

After the cage had been kept at 25 C and 65% humidity for 5 days, were the unsoldered flies are counted and the percentage mortality is calculated.

The results are shown in Table VI.

8 90

9 7S

N '- (4-chloro-O-tolyl) -N.N-dimeth \ 1-10 fbrmamidin (comparison)

Trial 6

Effective as an insecticide against small brown grasshoppers

Into an aqueous emulsion containing 0.05% of the test compound and by diluting an emulsifiable When concentrates with water had been prepared, young rice plants would last 30 seconds dipped and allowed to air dry. The rice plants thus prepared were placed in an experimental vessel introduced, in which small brown grasshoppers (Laodel phax striatellus traps) were kept. The test The vessel was closed with gauze and kept at 25 ° C. and a humidity of 65% for 48 hours Then the dead test animals were counted and the mortality in percent was calculated The results are shown in Table VII.

Table VII Table Vl

TcstvcrbindunE

Mortality in%

100 KK)

Test compound mortality

3 ^r > No. in%

4 90

8 70

N '- (4-chloro-O-tolyI) -C, N-dimethyl- 40 formamidine (comparison)

Claims (2)

Paienum> pniche: I. 5- H \ dro \\ laminomelh \ lenbarbitursäiirederi \ aie the general funnel I. NH -QR ₄ R ₁ ^:! C. N / N O O R, in which R ₁ and R _{2 are} each a water talom or an alkyl group with 1 to 4 carbon atoms. R 1 denotes an alkyl group having 1 to 3 carbon atoms and R ₄ denotes an ethyl or allyl group, as well as the metal salts of those of the above compounds in which at least one of the radicals R ₁ and R ₂ denotes a hydrogen atom. 2. Process for the preparation of the compounds according to claim 1, characterized in that one compound of the formula